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* UNITED, STATES f Paton tad September 20.. 1904.

PATENTcOFFICE.

nEPFio ucmqmcTun'Es on rHE LIKE. I

srncxncanou forming part of Letters Patent No; 770.533, dated Septemper20, 1904,

Application tiled in, a, 1902. Serial No.'109,196. (No speoimenaJ- To all whom, it may concern.

' Be it knowri that we, WILnn M Os'rwALn,

doctor of philosophy and professor, and Os- CAR. GRos, doctor of philosophy, both subjects of the German Emperor, and residents of Leipzig, in the Kingdom of Saxony, German Empire, have invented new and useful Improvements in Reproducing Pictures or the Like, of which the following is a full, clear, and exact specification, K I Our invention relates to a process depending upon reproduction by means of catalytic action. the modifications in the rapidity with which chemical processes proceed, these modifications being produced by substances that do not exist among the' substances produced by the chemical process. However, these substances may during the process participate in this process in any form-for instance, byin- 'termediate reaction'sand mayundergo secondary changementssuch as deposit of substances on the catalyzing surface, action on the reaction products, and the like. Another criterion of these catalyzing substances is that they are-in 'no stoechiometric relation to the.

reagents and reaction products. Now there are numerous substances possesslng these properties. Such substances are, for instance,-metals such as platinum and silver, metallic salts, compounds containing or forming hydrogen ions, compounds containingor forming hydroxyl ions, oxids. lnapplying the catalytic properties of these substances in the reproductiorf'ofpictures we proceed as follows: We form-first a picture or the like of the catalyzing substance. For-example,

a so-called platinum print produced by the ordinary photographic method may be used. Likewise silver,prints-for instance, the socalled salt-papersmay be used. Other than photochemical means may also be used for the production of the original picture or the like which is to act as a catalyzing agent. For example, a' drawing may be made with a saturated solution of ,potassium platiuum chlorid and this transformed into a drawing in metallic platinum by means of a saturated,

[ solution of potassium ferrous oxalate. Also paper may be covered with I a layer, of man:

By, catalytic action we understand gane se oxid ompounds by treatin'git with a Weaklyalkaline concentrated solution of potassium permanganate by means of a brush; I

Thissolution may be produced, for instance, by adding one gram of carbonate of soda to one hundred'cubic centimeters of saturated potassium permanganate solution. By drawing on this paper, after washing and "drying with a saturated oxalic-acid solution, after washing a drawingis produced lnwlnte lines on brown ground, which ground acts catalytlcally, while the lines do not. lhesc original pictures wethen use either for reproduction on paper or other carriers of the images mixture with which the paper or plate receiv ing the reproduction is covered, while in the indirect processes we. produce or destroy in certain points of the original, by means of the catalyzingaction, a substance which then reacts with other substances.

The follo wingexamples'will illustrate our process.

.Rcp i'otluction on tape 1' or the L'Ii/k.

I platinum than in other parts. ,W'hen the sub-' stances formed. by the reaction are coloringmatters or colors For. substances which by a suitable treatment maybe transformed intocolorin'g-matters or colors, orwhen such col-' bring-matters or colors or substances which jmay be transformed nto coloring-matters or colors are'decomposed by the reaction, alcol- 'ored print corresponding in all details with thepicture of theplatinum print is produced.

Example 1: Paper is impregnated witha'solut on containing from one-to five per cent. of

4 existing in every part.

per is pressed on .the. platinum original, there is't'ormed by chemical action in the parts in F contact with the platinum aproduct which is 1 redflcoloring-matter andby means of metallic salts may be transformed into other coloredsubstances. For instance, ferric sulfate, according to its concentration, transforms the x 0" mdeol-or into reddish browntoblackish gray.

.dn" this example other reactions of various.

kindsrwbich are influenced by catalysis may bez'substituted for that between potassium;

broniate and py'rogallol. Such reactions are,

"for instance, those between potassium bro:

- niate: and pyrocatechol, (by subsequent treatmentwith ferric sulfate blackish-blue pictu res being produced',) potassium bromate and gallie acidrpotassium chlorate and pyrogallol, 2o ipotassium nitrate and pyrogallol, hydrogen peroxid and pyrogallol, hydrogen peroxid and pyrocatechohhydrogen peroxid and gallic acid, hydrogen peroxid and anilin hydro: chlorid; orflthe like. i Exampleflz. Against a silver-bromid gelatin plate or a-silver-bromid paper which was exposed to theiaction of light fora moment we press a. platinum print impregnated with a- -saturated solution of potassium bromate.

Then in the parts where platinum'f exists the faction of light is neutralized, and a silver print- I g is obtained by developing in the usual manner.

Indirect prooess..For indirect -'reproduction by-me'ansof catalysis theori'ginals con- 3 5 -taining the catalyzing substance are treated with a solutionof substances which at the parts of the original containing the'catalyzing substance are more or less modified, acc0rd.-'

ingly to thequantit y of catalyzing'substance The original thus treated is then pressed either against paper or the like'impregnated with substances upon which the modified substance can act or against ordinarypaper'a-nd the like, the in-' visible image first produced then being developed by means of substances upon which the modified substances can act.

. Example 3: We pour a solution .of hydrogen peroxid over a platinum print. For instance, an ethereal solution may be used which is obtained by agitating an aqueous solution of hydrogen peroxid of thirty-threeper-cent. strength with twice its volume of ether and drying the ethereal solution by cooling down to 20 centigrade. At the parts containing platinum the hydrogen peroxid is destroyed .by catalytic action with a speed which is a function of the quantityof plati-' um existing at every part of the original.

o 'The platinum printtreated with hydrogen peroxid, as,above set forth, is then pressed, after voIatilization of the ether, for ten to forty seconds against a paper impregnated with-a saturated solution of ammonium ferb5 rous-sulfate.- The ferrous salt is then oxi- 1 This picture is a positive one if the print was negative.

-potassitimibr'omate and from five to twentyl dized to, ferric salt at the partswhere there live pe'r eentx of 'pyrogalloh When this pawas no platinum, andthe image can then be developed by variousmeans-for instance,

by, means of potassium ferrocyanid or gallic acid, tannin, pyrogallol, pyrocatechol, or the like, of one-half to one per cent. strength, for instance.

Example 4: The platinum print treated with hydrogen peroxid is pressed against paperimpregnated with a solution of a bichromate of five-per-cent. strength. An instable violet brown image is thusformed, which by treatmentwith a solution of potassium permamgmnateof one-per-cent. strength is transformed into a stable one consisting of manganese oxids.

Example 5: If theplatinum print treated with hydrogen peroxid is pressed against paper, an invisible print 0t hydrogen peroxid is obtained.v If. this invisible print is treated with a solution ofa manganese saltfor instance, of fifty partsof manganese sulfate in one hundred parts of water, containing or not a small excess of arnmon1a.a v1s1blep1cture formed of manganeseoxids is produced. platlnu in "Example. .6: If in the foregoing example a saturated "solution ofammonium ferrous sulfate is substituted for the manganese-salt solution and the printthentreated with a pyrogallol solution of aboutone-per-cent. strength, a'bla-ck print is obtained. Likewise other reactions influenced by hydrogen peroxid may be used.

Example'f: If the platinum print treated .with hydrogen peroxid, as above set forth,

is pressed upon sci-called rubber printing paper or .pigment printing-paper and this then treated with a saturated solution of ammonium ferroussulfate,,the rubber or-gela .tin is tanned atthe parts Where the hydrogen peroxid was not destroyed and becomes more or less insoluble, accordingly to the concentration; of .theperoxid. "The prints may then be developedin the usual manner.

In these-indirect processesmanganese-oxid originals produced, as above set forth, can be substituted forthe platinum prints. In these examples varicus materials other than paper may be, used ascarriers of the sensitive substances-as, for example, gelatin and the like. In the direct proeesssticking of such a gelatin film to the picture which is to be reproduced must be prevented by first tanning the gelatin; Other catalyzing agents may also be added to the sensitive substances, such agents acting alone only very slowly, but in conjunction with platinum and other catalyzing substances much more rapidly. This combination of different catalyzing agents may also 'be ettectedby impregnating, for instance, the

platinum original, with a solution of these slowly-acting agents.

Example 8: Copper sulfate may be used.

Its concentration may vary in both cases and 'ducingthe picture.

depends upon the time to be occupied in prolifth-per-cent. strength may be used.

Production of Printing-Plates.

we use substances which at the places in contact with the catalyzing substance produce a chemical action etching the metallic surface. Example 9: We impregnate a platinum print with a saturated solution of potassium f chlorate in acetic acid of from ten to fifty per cogper plate. Thecopper is dissolvedfrom th parts in'contactwit h the platinum of the. 1 original; 1 l

of gelatin. -"If'this platein then put into a. solution of ammonium ferrous 3. I fperoxid and a rilievo is obtainedwhich'can be i parts onlyret'ainingthese colors. Likewise cent. strength-and press itupon a polished 1hdirectp70cess.An original containing a the catalyzing substance is treated, as above set forth, with asubstance which is modified by the catalytic action and then caused to act upon the surface of the plate be used for prmting purposes. I

Example '10: A platinum print treated with hydrogen-peroxid. as set forth in Example 3, is pressed against aplate covered with a la er concentrated sulfate, the gelatin is tanned at the partswhere ferric salt i'sformed by the action of hydrogen used for printing with fatty colors,'the tanned Even a solution of one-" etched, eith'e Direct process-For etching metallic plates .vanic' current.

-forth. i

metallic plates may be etched indirectly. fThe metallic plate is then covered by means of the 35 catalytic action witlia coating of a substance J which is .either notattacked by acids or is not...

aconductoro electricity. The plate'is then Example 11: A platinum print'treated with hydrogen peroxid, as setforth in Example3,- is pressed against a metal plate covered with a layer of fish-glue containing a chromate.

The glue then becomes insoluble at the parts-45 v action, the degreeof this actionin the different '55 points being controlled by catalyzing agents contained intheoriginal, 'substantially'as set In testimony that we claim the-foregoing as our invention we have signed our names ii -16c presence of two-subscribing witnesses. 1

' -W1LHELM:0 STWA-LDL OSCAR GROS. Witnesses:

RUfDOLP ERIGKE, B. H. RN Jr. I

g as

r chemically or'by means of a'gal- Y i s, which consists in causing an original 

